Abstract

The Invar effect has remained at the forefront of materials research since Charles-´Edouard Guillaume discovered the vanishing thermal expansion of Fe-Ni alloys in 1897. More recently, a pressure-induced Invar effect was discovered in Fe-Ni alloys, and the relationship between classical and pressure induced Invar phenomena has added complexity to the century-old struggle to comprehend the microscopic origins of Invar behavior.
In this thesis I present our recent discovery of pressure-induced Invar behavior in Pd3Fe with the ordered L12 structure. Nuclear forward scattering measurements show that the ferromagnetic ground state in Pd3Fe is destabilized with pressure, collapsing around 10GPa (V/V0=0.96) to a lowspin magnetic state. From high-pressure synchrotron x-ray diffraction measurements we find a large volume collapse at ambient temperature to accompany the collapse of ferromagnetism. After the volume collapse there is a significant increase in the bulk modulus. Using nuclear resonant inelastic x-ray scattering to study the 57Fe phonon partial density of states (PDOS) at high pressures, we find the pressure-induced magnetic transition to cause an anomalous relative softening of the average phonon frequency. Heating our sample to 650K in a furnace at a pressure of 7GPa, synchrotron xray diffraction measurements reveal negligible thermal expansion from 300 to 523 K, demonstrating pressure-induced Invar behavior in Pd3Fe.
Density functional theory calculations identify a ferromagnetic ground state in Pd3Fe with large moments at the Fe sites. These calculations show that the application of pressure counteracts the band-filling effect of Pd. By tuning the position of the top of the 3d band with respect to the Fermi level, pressure-induced Invar behavior resembles classical Invar behavior that is controlled by chemical composition. This insight marks the first step towards a unification of our understanding vii of classical and pressure-induced Invar behavior. Pressure drives the majority-spin t2g antibonding electronic states closer to the Fermi level. The transition to the low-spin state occurs as these t2g states move across the Fermi level, transferring charge to the minority-spin eg nonbonding electronic states. This charge transfer reduces the internal electronic pressure in the material, giving a volume reduction in the low-spin state. The movement of the t2g states with increasing pressure results in a greater number of states at the Fermi level, increasing screening efficiency and softening the first nearest-neighbor Fe-Pd longitudinal force constants in the low-spin state. The measured and calculated magnetic transition pressures differ significantly, despite sharing similar elastic properties in both the ferromagnetic and low-spin states. The magnitude of the disagreement between theoretical and experimental magnetic transition pressures suggests a spin-disordered state exists at high pressures in Pd3Fe. A shape discrepancy between the calculated and measured high-pressure Fe PDOS suggests significant short-range spin correlations exist in this spin-disordered state.